Potential of zero total charge of platinum single crystals: A local approach to stepped surfaces vicinal to Pt(111)

The electrochemical behavior of platinum single-crystal electrodes is revisited, with special emphasis on the determination of the potential of zero charge. We show that the measure of the charge displaced during CO adsorption allows the determination of the potential of zero total charge (PZTC). The estimation of the potential of zero free charge (PZFC) is discussed, with different degrees of approximation. The application of this methodology to the study of the PZTC of platinum stepped surfaces vicinal to Pt(111) reveals a marked decrease of the PZTC due to the introduction of surface steps. This effect is interpreted as the result of the existence of markedly smaller surface potentials localized on step sites. The importance of considering local aspects of the interface is emphasized with the use of N₂O reduction as a sensitive probe to the local structure of the surface. It is proposed that the different local maxima observed in the absolute value of the reduction current correspond to the local values of PZTC. It is shown that there is, in general, good agreement between the overall PZTC, obtained from the CO displacement, and that calculated from the local values inferred from the N₂O reduction. Further insight is obtained with the application of the laser-induced temperature jump method. This technique is useful to calculate the potential of maximum entropy of the double-layer formation. The resulting value of this potential for Pt(111) is discussed in the light of the PZFC value obtained from different approaches. For stepped surfaces vicinal to Pt(111), two local maxima in the entropy of the double layer are observed that are close to the local PZTC values estimated from the N₂O reduction. This result suggests the existence of cooperative effects in the organization of the water dipoles close to the electrode surface. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1275–1292. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

A computational study of the LiH dimer

A theoretical study of the properties of the linear LiH dimer was undertaken. In this dimer, an unusual type of hydrogen bonding (termed "inverse" hydrogen bonding by some authors), which involves the hydrogen bonded molecule acting as an electron donor (rather than as a proton donor), is exhibited. The optimized geometry, dipole moment, interaction energy, atomic charges, harmonic vibrational frequencies, and frequency shifts for the dimer are computed at the SCF, MP2, and QCISD levels of theory using mainly a 6-31++G(d,p) basis set. We also examined the relative stability of the mono-deuterated isotopomers of linear (LiH)(2), i.e., Li-H...Li-D and Li-D...Li-H. Analysis of the normal vibrational modes, changes in the partial atomic charges, and changes in the vibrational frequencies of LiH on complexation were used to gain insight into the bonding and properties of the linear LiH dimer and its isotopomers.     

ELECTRON PARAMAGNETIC RESONANCE STUDIES OF SINGLE CRYSTAL SODIUM HEXAMOLYBDOCHROMATE (Ⅲ)Cr~(3+)/Na_3(AlMo_6O_(24)H_6)·8H_2O

An X-band EPR study on a Na_3(CrMo_6O_(24)H_6)·8H_2O single crystal diluted by its isomor-phic compound Na_3(AlMo_6O_(24)H_6)·8H_2O at room temperature is reported. Using the least squares-fitting method to simulate the EPR data for principal planes, the Hamiltonian parameterswere obtained. The principal values of the g tensors are g_(ZZ) = 1.904, g_(XX)= 1.973, g_(YY)=1.933. The zero field splitting tensor parameters are D = 0.275 cm~(-1), E = 0.05 cm~(-1). The fielddependence of Cr~(3+) energy levels with field at different angles from the principal axes whenthe field is along the principal planes is calculated based on these experimental parameters.The isofrequency plots of calculated field vs. angle are also shown. They agree well with theexperimental results.     

A universal constant for the convergence of Newton's method and an application to the classical homotopy method

We give a new theorem concerning the convergence of Newton's method to compute an approximate zero of a system of equations. In this result, the constanth ₀=0.162434... appears, which plays a fundamental role in the localization of good initial points for the Newton iteration. We apply it to the determination of an appropriate discretization of the time interval in the classical homotopy method.     

雪崩光电探测器的击穿效应模型分析

基于CMOS工艺制备了空穴触发的Si基雪崩探测器(APD),基于不同工作温度下器件的击穿特性,建立空穴触发的雪崩器件的击穿效应模型。根据雪崩击穿模型和击穿电压测试结果,拟合曲线得到击穿电场与温度的关系参数(dE/dT),器件在250～320 K区间内,击穿电压与温度是正温度系数,器件发生雪崩击穿为主,dV/dT=23.3 mV/K,其值是由倍增区宽度以及载流子碰撞电离系数决定的。在50～140 K工作温度下,击穿电压是负温度系数,器件发生隧道击穿,dV/dT=-58.2 mV/K,其值主要受雪崩区电场的空间延伸和峰值电场两方面因素的影响。     

Ka频段高灵敏度检波器研制

介绍了一种高电压灵敏度、低切线灵敏度检波器的设计方法。在建立检波二极管简化物理模型的基础上,进行了检波二极管Ka频段阻抗参数的提取,再根据提取的阻抗参数,通过仿真优化了射频匹配网络,使得检波器能够较好地工作在23～34 GHz。实测表明,在1.2 kHz视频带宽下,当输入功率为-30 dBm时,23～34 GHz范围内电压灵敏度高于6 000 mV/mW,切线灵敏度优于-56 dBm,对应等效噪声功率(Noise Equivalent Power, NEP)估算为11.5～36 pW/Hz^1/2。对比实测与仿真结果较为一致,证明了阻抗参数提取的有效性。     

光纤电压传感器传感头优化与热致非互易误差抑制

针对普通光纤电压传感器在外界温度扰动下其输出精度和稳定性会受到严重影响这一问题,本文提出了一种采用保偏光子晶体光纤(polarization maintaining photonic crystal fiber,PM-PCF) 作为传感光纤的传感头优化方法抑制温度扰动下的系统非互易误差。在综合考虑PM-PCF与传统熊猫型保偏光纤(panda polarization maintaining fiber,panda-PMF) 尾纤间的熔接损耗、传输损耗以及现有工艺条件下的光纤制备等问题的基础上,优化得到了与panda-PMF间的熔接损耗低至0.14 dB的PM-PCF;并对比分析了这两种保偏光纤的双折射温度依赖特性,建立了全光纤类型的光学电压传感器(fiber optic voltage sensor,FOVS) 热致系统误差输出模型,分析验证了PM-PCF在解决反射式逆压电型FOVS热致非互易问题的可行性。结果表明,采用PM-PCF优化后的FOVS热致非互易误差约是传统保偏光纤电压传感器 的10-2量级。这在提高系统输出精度和稳定性等方面具有显著优势,同时这种低损耗的优化方法在光纤传感及通信等领域具有重要的应用价值。     

Sufficient Utilization of Mn2+/Mn3+/Mn4+ Redox in NASICON Phosphate Cathodes towards High-Energy Na-Ions Batteries

Na superionic conductor of Na₃MnTi(PO₄)₃ only containing high earth-abundance elements is regarded as one of the most promising cathodes for the applicable Na-ion batteries due to its desirable cycling stability and high safety. However, the voltage hysteresis caused by Mn²⁺ ions resided in Na⁺ vacancies has led to significant capacity loss associated with Mn reaction centers between 2.5–4.2 V. Herein, the sodium excess strategy based on charge compensation is applied to suppress the undesirable voltage hysteresis, thereby achieving sufficient utilization of the Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. These findings indicate that the sodium excess Na_3.5MnTi_0.5Ti_0.5(PO₄)₃ cathode with Ti⁴⁺ reduction has a lowest Mn²⁺ occupation on the Na⁺ vacancies in its initial composition, which can improve the kinetics properties, finally contributing to a suppressed voltage hysteresis. Based on these findings, it is further applied the sodium excess route on a Mn-richer phosphate cathode, which enables the suppressed voltage hysteresis and more reversible capacity. Consequently, this developed Na_3.6Mn_1.15Ti_0.85(PO₄)₃ cathode achieved a high energy density over 380 Wh kg⁻¹ (based on active substance mass of cathode) in full-cell configurations, which is not only superior to most of the phosphate cathodes, but also delivers more application potential than the typical oxides cathodes for Na-ion batteries.     

Long Duration Persistent Photocurrent in 3 nm Thin Doped Indium Oxide for Integrated Light Sensing and In-Sensor Neuromorphic Computation

Miniaturization and energy consumption by computational systems remain major challenges to address. Optoelectronics based synaptic and light sensing provide an exciting platform for neuromorphic processing and vision applications offering several advantages. It is highly desirable to achieve single-element image sensors that allow reception of information and execution of in-memory computing processes while maintaining memory for much longer durations without the need for frequent electrical or optical rehearsals. In this work, ultra-thin (<3 nm) doped indium oxide (In₂O₃) layers are engineered to demonstrate a monolithic two-terminal ultraviolet (UV) sensing and processing system with long optical state retention operating at 50 mV. This endows features of several conductance states within the persistent photocurrent window that are harnessed to show learning capabilities and significantly reduce the number of rehearsals. The atomically thin sheets are implemented as a focal plane array (FPA) for UV spectrum based proof-of-concept vision system capable of pattern recognition and memorization required for imaging and detection applications. This integrated light sensing and memory system is deployed to illustrate capabilities for real-time, in-sensor memorization, and recognition tasks. This study provides an important template to engineer miniaturized and low operating voltage neuromorphic platforms across the light spectrum based on application demand.     

Voltage Decay of Li-Rich Layered Oxides: Mechanism,Modification Strategies,and Perspectives

Li-rich layered oxides (LLOs) have been considered as the most promising cathode materials for achieving high energy density Li-ion batteries. However, they suffer from continuous voltage decay during cycling, which seriously shortens the lifespan of the battery in practical applications. This review comprehensively elaborates and summarizes the state-of-the-art of the research in this field. It is started from the proposed mechanism of voltage decay that refers to the phase transition, microscopic defects, and oxygen redox or release. Furthermore, several strategies to mitigate the voltage decay of LLOs from different scales, such as surface modification, elemental doping, regulation of components, control of defect, and morphology design are summarized. Finally, a systematic outlook on the real root of voltage decay is provided, and more importantly, a potential solution to voltage recovery from electrochemistry. Based on this progress, some effective strategies with multiple scales will be feasible to create the conditions for their commercialization in the future.